Anthraquinone dyes and method of use

ABSTRACT

The present invention relates to anthraquinone compounds of formula I, ##STR1## in which R 1  is alkyl or cycloalkyl, 
     R 2  is hydrogen, methyl or ethyl, 
     R 3  is hydrogen or methyl, 
     either 
     R 4  is hydrogen, methyl or ethyl, and Y--CO-- is the radical of an organic aliphatic aromatic or araliphatic carboxylic acid containing a total of 2 to 12 carbon atoms, 
     or 
     R 4  together with the radical Y--CO-- and the nitrogen atom to which they are bound signify a cyclic imide of a dicarboxylic acid containing a total of 4 to 8 carbon atoms, 
     X is a direct bond or (C 1-3 )alkylene, 
     n is 0 or 1 
     which compounds are useful as colorants. More particularly those compounds where n is 1 are useful as anionic dyestuffs and those compounds where n is 0 are useful as pigments.

The present invention relates to anthraquinone compounds, theirproduction and use as dyes.

More particularly, the present invention relates to compounds of formulaI, ##STR2## in which

R₁ is alkyl or cycloalkyl,

R₂ is hydrogen, methyl or ethyl,

R₃ is hydrogen or methyl,

either

R₄ is hydrogen, methyl or ethyl, and Y--CO-- is the radical of anorganic aliphatic aromatic or araliphatic carboxylic acid containing atotal of 2 to 12 carbon atoms,

or R₄ together with the radical Y--CO-- and the nitrogen atom to whichthey are bound signify a cyclic imide of a dicarboxylic acid containinga total of 4 to 8 carbon atoms,

X is a direct bond or (C₁₋₃)alkylene,

n is 0 or 1

which compounds, where n is 1, are in free acid or salt form.

Where R₁ is alkyl it may be primary, secondary or tertiary. When R₁ is aprimary alkyl radical this may be linear or branched, preferably thelatter, and advantageously contains 1 to 12, preferably 1 to 9,especially 6 to 9 carbon atoms. Where R₁ is a secondary alkyl radicalsuch radical preferably contains 3 to 12, more preferably 3 to 9 andespecially 6 to 9 carbon atoms. When R₁ is a tertiary alkyl radical suchradical preferably contains 4 to 12 and more preferably 6 to 9 carbonatoms.

Where R₁ is cycloalkyl it is preferably cyclohexyl which isunsubstituted or substituted by a total of up to three lower alkylgroups and the total number of carbon atoms in such substitutedcyclohexyl is up to 12, preferably up to 9. Preferably any cycloalkyl asR₁ is cyclohexyl which is optionally substituted by 1 to 3 methylgroups. More preferably any cycloalkyl as R₁ is unsubstitutedcyclohexyl, 2-,3- or 4-methylcyclohexyl, 2,3-dimethylcyclohexyl or3,3,5-trimethylcyclohexyl, with unsubstituted cyclohexyl beingespecially preferred.

R₁ is preferably R₁ ', where R₁ ' is a primary (C₁₋₉)-alkyl, secondary(C₃₋₉)alkyl or cyclohexyl which is optionally substituted by up to threemethyl groups.

More preferably R₁ is R₁ ", where R₁ " is secondary (C₃₋₉)-alkyl orcyclohexyl which is optionally substituted by up to three methyl groups.

Most preferably R₁ is R₁ '", where R₁ '" is secondary (C₆₋₉)-alkyl orcyclohexyl which is optionally substituted by up to three methyl groups,with cyclohexyl or substituted cyclohexyl being especially preferred.

Any methyl as R₂ is preferably para to the --NH-- group.

R₂ is preferably R₂ ', where R₂ ' is hydrogen or methyl in the positionpara to the --NH-- group. More preferably R₂ is hydrogen.

R₃ is preferably hydrogen.

R₄ is preferably R₄ ', where R₄ ' is hydrogen, methyl or ethyl ortogether with --N--CO--Y forms phthalimide. More preferably R₄ is R₄ "where R₄ " is hydrogen or together with --N--CO--Y forms phthalimide.Most preferably R₄ is hydrogen.

Y--CO-- as the radical of an aliphatic, aromatic or araliphaticcarboxylic acid may contain hetero atoms such as oxygen, nitrogen orsulphur and further may bear substituents which may be split off asanions especially halogen atoms, or may bear non-ionogenic substituentssuch as alkyl or alkoxy groups provided that the total number of carbonatoms in the group Y is not greater than 11. Preferably, however, thegroup Y contains no hetero atoms and no further substituents exceptthose which may be split off as anions. Where Y--CO-- is the radical ofan aromatic carboxylic acid, the aromatic nucleus is preferably phenylor phenyl monosubstituted by chloro, bromine or methyl, especiallyphenyl. Where Y--CO-- is the radical of an aliphatic carboxylic acidthis also includes cycloaliphatic carboxylic acid radicals. Thepreferred cycloaliphatic radical is cyclohexyl. Preferably, however, anyaliphatic carboxylic acid radical is open chain and may be saturated orethylenically unsaturated. Thus, when Y is aliphatic it is preferably(C₁₋₇), more preferably (C₁₋₄), most preferably (C₁₋₂)alkyl optionallysubstituted by halogen or is (C₂₋₅), more preferably (C₂₋₃)alkenyloptionally substituted by halogen especially those alkenyl radicalswhere the double bond is between the α and β carbon atoms. When Y isalkyl or alkenyl such groups are preferably unsubstituted or substitutedby one or two halogen atoms, one of which is on the α-carbon atom.

By halogen is to be understood chlorine or bromine.

The preferred halogen is chlorine.

Preferably Y is Y' and R₄ is R₄ ' where either, Y' is phenyl; or phenylmonosubstituted by methyl, chlorine or bromine; (C₁₋₇)alkyl; (C₁₋₇)alkylsubstituted by up to two halogen atoms; (C₂₋₅)alkenyl; (C₂₋₅)alkenylsubstituted by up to two halogen atoms; or cyclohexyl and R₄ ' ishydrogen, methyl or ethyl or, Y'--CO together with R₄ ' and the nitrogenatom forms phthalimide.

More preferably Y is Y" and R₄ is R₄ " where either, Y" is phenyl,##STR3## and R₄ " is hydrogen or, Y"--CO and R₄ " together with thenitrogen atom form phthalimide.

Even more preferably Y is Y'", where Y'" is ##STR4## with --CH₂ Cl beingmost preferred.

When X is a direct bond it is preferably para to the --NH-- group. WhenX is alkylene, the alkylene group may be in any position relating to the--NH-- group, however, preferably any alkylene as X is ortho or para tothe --NH-- group, more preferably ortho, especially with X is methylene.

Preferably X is X', where X' is ##STR5## More preferably X is X", whereX" is ##STR6## especially --CH₂ --.

Preferred compounds of formula I are those of formula I' ##STR7##

in which R₁ ', R₂ ', R₄ ', X' and Y' are as defined above.

More preferred compounds are those of formula I' where R₁ ' is R₁ ", Y'is Y" and R₄ ' is R₄ ", especially those wherein X' is X".

Even more preferred compounds are those of formula I', in which R₁ ' isR_(1"') and R₄ ' is hydrogen, especially those when X' is X".

The most preferred compounds of formula I are those of formula I"##STR8## especially those wherein Y'" is --CH₂ Cl.

Of the compounds of formulae I, I' and I" those in which n is 1 arepreferred, especially the salts thereof.

When n is 1 and the compounds of formula I are in the salt form, thecation of the salt form of the sulpho group is not critical and may beany non-chromophoric cation common in anionic dyestuffs. Examples ofsuitable cations are sodium, lithium, potassium, ammonium, mono-, di- ortriethanolammonium or mono-, di- or triisopropanolammonium.

The present invention further provides a process for the production of acompound of formula I, as defined above, comprising reacting a compoundof formula II, ##STR9## with a compound of formula III, ##STR10##wherein

Z is a leaving group, and

R₄ is as defined above and where n is 1, sulphonating the resultingproduct.

Suitably, Z is hydroxyl or halogen. Preferably Z is hydroxyl. Thereaction is carried out in accordance with known methods. Preferably thereaction is carried out in the presence of 90-100% more preferably92-98% sulphuric acid. Suitable reaction temperatures are in the rangeof from 0° to 30° C., preferably 15° to 25° C. The product obtained maybe separated in accordance with known procedures. When a compound offormula I in which n is 1 is desired, the product of the reaction of acompound of formula II with a compound of formula III may be sulphonatedwithout isolation from the reaction mixture. However, it is preferred toisolate the product before carrying out the sulphonation step.

Sulphonation may be carried out in accordance with known methods.Preferably oleum is employed, especially 10-65%, more preferably 20-50%oleum. Suitable sulphonation temperatures are in the range of from 0° to25° C., preferably 0° to 5° C. The sulphonated product may be isolatedin accordance with known methods and may be neutralized if the salt formof the compounds of formula I is desired.

The compounds of formula II and III are either known or may be preparedin accordance with known methods from available starting materials.

The compounds of formula I are useful as dyestuffs. More particularly,the compounds of formula I wherein n is 0 are useful as pigments fordyeing synthetic or semisynthetic, hydrophobic organic substrates in themass. Suitable such substrates include polyester, viscose, polyolefinsor synthetic polyamides. The compounds of formula I where n is 1 areuseful as dyestuffs for dyeing or printing anionic dyeable, especiallytextile, substrates. Suitable such substrates include natural orregenerated cellulose, natural or synthetic polyamides, polyurethanes orbasically modified polyolefins. The preferred substrates are natural orsynthetic polyamides. The substrate may be in fibre, fabric or yarnform.

Dyeing or printing may be carried out in accordance with known methods.The dyestuffs wherein n is 1 may be mixed with blending agents such asdextrin.

The compounds of formula I where n is 1, especially when in salt form,are well water-soluble resistant to the action of salts and of hardwater. They also build-up on synthetic polyamides from a neutral toweakly acid bath. The dyeings and prints obtained therewith are even,brilliant blue and possess notable light fastness and wet fastnesses.The dyes may be used for dyeing alone or in admixture with other dyeshaving similar properties.

The following Examples further serve to illustrate the invention. In theExamples, all parts and percentages are by weight and the temperaturesare in degrees Centigrade.

EXAMPLE 1

A mixture of 40 g of1-methoxy-4-(2'-benzylocyclohexylamino)-anthraquinone and 120 ml2,3-dimethylcyclohexylamine is stirred for 10 hours at 135°. The mixtureis then allowed to cool to 50° and 100 ml of methanol are added thereto.The mixture is cooled such that the reaction product precipitates. Afterfiltration and washing with methanol a compound of formula ##STR11## isobtained.

10.4 g of this compound is mixed well with 3 gN-methylene-chloroacetamide and added portionwise to 50 g 95% sulphuricacid at a temperature of 12° to 14°. The mixture is stirred for 3 hoursat this temperature, subsequently 50 g 65% oleum is added dropwise at atemperature of 0° to 3° and the whole is stirred for 4 hours. Themixture is poured onto ice, the precipitated dyestuff is filtered andwashed with an 8% potassium chloride solution. The product which in thefree acid form is of formula ##STR12## is made into a paste with alittle water, adjusted to a pH value of 7 with potassium hydroxide anddried at 50° in vaccuo. The dyestuff has good water solubility and dyeswool and synthetic polymaides in very brilliant blue shades. The dyeingshave good light- and wet fastnesses.

EXAMPLE 2

Instead of the 2,3-dimethylcyclohexylamine used in Example 1, the sameamount of 3,3,5-trimethylcyclohexylamine is employed following the sameprocedure as described in Example 1. The product obtained is of formula##STR13## and has good water solubility and also dyes syntheticpolyamides and wool in very brilliant blue shades. The dyeings have goodlight- and wet fastnesses.

EXAMPLE 3

A homogeneous mixture of 10.5 g of the compound of formula ##STR14## and3 g N-methylol-chloroacetamide is added, at a temperature of 18° to 22°,to 50 g of 92% sulphuric acid. The reaction mixture is stirred at thistemperature for 2 hours and then poured onto ice. The precipitate of thecondensation product is filtered and the filter cake is washed withwater until the filtrate has a pH value of 6.5 to 7. The product isdried in vaccuo at 60° and then is dissolved in 50 g of 25% oleum at 0°to 5°. The mixture is stirred for 2 hours at this temperature and isthen poured onto ice. The precipitate is filtered and the filter cake iswashed with a 10% sodium chloride solution. The product, which in thefree acid form, is of formula ##STR15## is added to water and lithiumhydroxide is added to give a pH value of 7. The dye solution isevaporated to dryness in a vaccuum at 60°. A blue powder is obtainedwhich gives dyeings on wool and nylon of brilliant blue shades havinggood wet fastnesses. The dyestuff has good water solubility and isresistant to the action of salts and lime. The sodium salt form orpotassium salt form of the dye may be made in analogous manner.

EXAMPLE 4

A mixture of 19 g quinizarin, 5 g leucoquinizarin, 20 ml2-benzylcyclohexylamine and 80 ml chlorobenzene is stirred in a nitrogenatmosphere at a temperature of 130° for 10 hours. 50 ml cyclohexylamineare added thereto and the whole is stirred at a temperature of 125° for12 hours. The temperature is allowed to drop to 65° and then 40 mlethylalcohol are added thereto whereby the reaction productprecipitates. The latter is filtered and washed with ethylalcohol. 10 gof the 1-cyclohexylamino-4-(2'-benzylcyclohexylamino)anthraquinone,after recrystallization from isopropanol, are mixed with 3 gN-methylol-chloroacetamide and following the procedure of Example 3 adyestuff, which in the free acid form, is of formula ##STR16## isobtained. The dyestuff in the lithium-, potassium- and sodium salt formhas good water solubility and gives even dyeings on wool and syntheticpolyamides from a neutral to weakly acid dyebath. The dyeings have goodlight- and wet fastnesses such as fastness to water, washing, sweat andmilling.

In the following Table further anthraquinone dyestuffs which may beprepared in analogy with the procedure described in Example 3, aregiven. They correspond, in the free acid form to formula ##STR17## Thedyestuffs in the lithium-, sodium- and potassium salt form have goodwater solubility and dye wool and synthetic polyamides in brilliant blueshades.

                                      TABLE                                       __________________________________________________________________________     No.Example                                                                         R.sub.x                                                                                           ##STR18##         R.sub.z                           __________________________________________________________________________     5                                                                                  ##STR19##                                                                                         ##STR20##        NHCOCH.sub.2 Br                     6   "                   "                 NHCOCHCH.sub.2                      7   "                   "                                                                                                ##STR21##                          8   "                   "                                                                                                ##STR22##                          9   "                   "                                                                                                ##STR23##                         10   "                   "                 NHCOCH.sub.2CH.sub.3               11   "                   "                 NHCOCH.sub.2 CH.sub.2 CH.sub.3                                                8                                  12   "                   "                                                                                                ##STR24##                         13   "                   "                                                                                                ##STR25##                         14   "                   "                                                                                                ##STR26##                         15 to 24                                                                            ##STR27##          "                 as Examples 5 to 14                25 to 34                                                                            ##STR28##          "                 as Examples 5 to 14                35                                                                                  ##STR29##          "                 NHCOCH.sub.2 Cl                    36                                                                                  ##STR30##          "                 "                                  37                                                                                  ##STR31##          "                 "                                  38                                                                                  ##STR32##          "                 "                                  39                                                                                  ##STR33##          "                 "                                  40                                                                                  ##STR34##                                                                                         ##STR35##        "                                  41                                                                                  ##STR36##          "                 "                                  42                                                                                  ##STR37##          "                 "                                  43                                                                                  ##STR38##          "                 "                                  44                                                                                  ##STR39##          "                 "                                  45                                                                                  ##STR40##          "                 "                                  46                                                                                  ##STR41##          "                 "                                  47                                                                                  ##STR42##          "                 "                                  48                                                                                  ##STR43##                                                                                         ##STR44##        "                                  49                                                                                  ##STR45##          "                 "                                  50                                                                                  ##STR46##          "                 "                                  51                                                                                  ##STR47##          "                 "                                  52                                                                                  ##STR48##                                                                                         ##STR49##        "                                  53                                                                                  ##STR50##          "                 "                                  54                                                                                  ##STR51##          "                 "                                  55                                                                                  ##STR52##          "                 "                                  56                                                                                  ##STR53##          "                 "                                  57                                                                                  ##STR54##          "                 "                                  58                                                                                  ##STR55##          "                 "                                  59 to 65                                                                           as Examples 52 to 58                                                                               ##STR56##        "                                  66 to 72                                                                           as Examples 52 to 58                                                                               ##STR57##        "                                  73 to 79                                                                           as Examples 52 to 58                                                                               ##STR58##        "                                  80 to 86                                                                           as Examples 52 to 58                                                                               ##STR59##        "                                  87                                                                                  ##STR60##                                                                                         ##STR61##        "                                  88                                                                                  ##STR62##          "                 "                                  89                                                                                  ##STR63##          "                 "                                  90                                                                                  ##STR64##          "                 "                                  91                                                                                  ##STR65##          "                 "                                  92 to 96                                                                           as Examples 87 to 91                                                                               ##STR66##        "                                  __________________________________________________________________________

Application Example

1 Part of the dye prepared as described in Example 1 is dissolved indyebath containing 6000 parts water at 40°; subsequently 4 partsammoniumsulphate are added thereto. 100 Parts Nylon 66 yarn are added tothe dyebath which is heated to the boil over a period of 30 minutes andheld at this temperature for 1 hour. The dyed substrate is removed,rinsed and dried. A brilliant blue even dyeing is obtained.

Wool may be dyed in accordance with the same procedure.

In analogy with the above procedure the dyes of Examples 2 to 96 may beused to dye Nylon 66 and wool.

What is claimed is:
 1. A compound of formula I, ##STR67## in which R₁ isalkyl or cycloalkyl,R₂ is hydrogen, methyl or ethyl, R₃ is hydrogen ormethyl, R₄ is hydrogen, methyl or ethyl, and Y--CO-- is the radical ofan organic aliphatic aromatic or araliphatic carboxylic acid containinga total of 2 to 12 carbon atoms, X is a direct bond or (C₁₋₃)alkylene, nis 0 or 1which compound, where n is 1, is in free acid or salt form. 2.A compound according to claim 1, in which X is ##STR68##
 3. A compoundaccording to claim 1, in which Y is Y' and R₄ is R₄ ', where either, Y'is phenyl; methylphenyl; chlorophenyl; bromophenyl; (C₁₋₇)alkyl;(C₁₋₇)alkyl substituted by up to two halogen atoms; (C₂₋₅)alkenyl;(C₂₋₅)alkenyl substituted by up to two halogen atoms; or cyclohexyl andR₄ ' is hydrogen, methyl or ethyl.
 4. A compound according to claim 3,in which any alkyl as Y' contains 1 to 4 carbon atoms.
 5. A compoundaccording to claim 4, in which any alkyl as Y' contains 1 to 2 carbonatoms and any alkenyl contains 2 or 3 carbon atoms.
 6. A compoundaccording to claim 1, in which R₁ is a primary (C₁₋₉)alkyl, secondary(C₃₋₉)alkyl or cyclohexyl which is optionally substituted by up to threemethyl groups, R₂ is hydrogen or methyl in a position para to the --NH--group and R₃ is hydrogen.
 7. A compound according to claim 6, in which Yis Y" and R₄ is R₄ ", where either Y" is phenyl, ##STR69## and R₄ " ishydrogen.
 8. A compound according to claim 7 wherein X is ##STR70##
 9. Acompound according to claim 5, in which R₁ is R₁ '", where R₁ '" issecondary (C₆₋₉)alkyl or cyclohexyl which is optionally substituted byup to three methyl groups.
 10. A compound according to claim 9, offormula I" ##STR71## in which R'" is as defined in claim 9 and Y'" is##STR72##
 11. A compound according to claim 10, in which R₁ iscyclohexyl, 2-, 3-, or 4-methylcyclohexyl, 2,3-dimethylcyclohexyl,3,3,5-trimethylcyclohexyl, or secondary (C₆₋₉)alkyl.
 12. A compoundaccording to claim 10, in which R₁ is other than (C₆₋₉)secondary alkyl.13. A compound according to claim 6, in which X is ##STR73##
 14. Acompound according to claim 1, in which R₁ is secondary (C₃₋₉)alkyl orcyclohexyl which is optionally substituted by up to three methyl groups.15. A compound according to claim 1, in which n is
 1. 16. A compoundaccording to claim 1, of formula, ##STR74## or of formula, ##STR75## orof formula, ##STR76## in free acid or salt form.
 17. A compoundaccording to claim 1 wherein R₁ is primary alkyl of 1 to 12 carbonatoms, secondary alkyl of 3 to 12 carbon atoms, tertiary alkyl of 4 to12 carbon atoms, unsubstituted cyclohexyl or cyclohexyl substituted byup to 3 lower alkyl groups such that the total number of carbon atoms insuch substituted cyclohexyl is up to
 12. 18. A compound according toclaim 17 wherein Y contains no hetero atoms and is either unsubstitutedor bears substituents which may split off as anions.
 19. A compoundaccording to claim 17 wherein any substituent on Y is chlorine orbromine.
 20. A compound according to claim 1, 7, 9, 18 or 8 wherein Y isY'" wherein Y'" is ##STR77##